Methods of inhibiting corrosion with ethane diphosphonate compositions

ABSTRACT

WHEREIN R1 and R2 are hereinafter defined and R3 is hydrogen or a metal ion and n is an integer having a value of 1 or 2, along or in combination with zinc, dichromate, certain thiols and 1,2,3-triazoles and mixtures thereof, are disclosed as inhibiting the corrosion of metals by oxygen-bearing waters.   Ethane diphosphonates having the formula

States Patent 1 King et al.

1 1 Jan. 30, 1973 l54l METHODS OF INHIBITING CORROSION WITH ETHANE DIPHOSPHONATE COMPOSITIONS [75] inventors: Thomas M. King, St. Louis; Howard L. Vandersall, Ballwin, both of Mo.

[73] Assignee: Monsanto Company, St. Louis, Mo.

[22] Filed: April 13, 1970 [21] Appl. No.: 27,982

[52] U.S. Cl ..252/389 A, 2l/2.7, 106/14, 210/58, 252/855 E, 252/181, 252/387,

[51] InLCl. ..C23f1l/l0,C23f1l /l6 [58] Field of Search ..252/389 A,387, 181, 389 R, 252/855 E; 2l/2.7, 2.5; 106/14; 260/5024 3,625,716 12/1971 King et al. ..260/502.4 P 3,654,151 4/1972 King et a1, 260/5024 P 3,664,975 5/1972 Kerst ..260/502.4 P

Primary Examiner-Leon D. Rosdol Assistant Examinerlrwin Gluck Attorney-Herbert B. Roberts, Roger R. Jones, James J. Mullen and Neal E. Willis [57] ABSTRACT Ethane diphosphonates having the formula 0 R1 R2 i ORQ l o 1 ORa ()Rs wherein R, and R are hereinafter defined and R is hydrogen or a metal ion and n is an integer having a value of l or 2, along or in combination with zinc, dichromate, certain thiols and 1,2,3-triazoles and mixtures thereof, are disclosed as inhibiting the corrosion of metals by oxygen-bearing waters.

31 Claims, No Drawings METHODS OF INHIBITING CORROSION WITH ETHANE DIPHOSPHONATE COMPOSITIONS The present invention relates to corrosion inhibiting compositions and to methods of inhibiting the corrosion of metal surfaces in contact with an aqueous medium of a corrosive nature. More particularly, this invention relates to methods of inhibiting the corrosion of metal surfaces by utilizing in the corrosive aqueous medium an ethane diphosphonate either alone or in combination with a water-soluble zinc salt, a dichromate, certain thiols, 1,2,3-triazoles and mixtures thereof.

The present invention has special utility in the prevention of the corrosion of metals which are in contact with circulating water, that is, water which is moving through condensers, engine jackets, cooling towers or distribution systems, however, it can be used to prevent the corrosion of metal surfaces in other aqueous corrosive media. This invention is especially valuable in inhibiting the corrosion of ferrous metals includ ing iron and steel (also galvanized steel) and non-ferrous metals including copper and its alloys, aluminum and its alloys and brass. These metals are generally used in circulating water systems.

The major corrosive ingredients of aqueous cooling systems are primarily dissolved oxygen and inorganic salts, such as the carbonate, bicarbonate, chloride and/or sulfate salts of calcium, magnesium and/or sodi- It is, therefore, a primary object of this invention to provide new corrosion inhibiting methods.

It is another object of this invention to provide new corrosion inhibiting methods for ferrous metals including iron and steel and non-ferrous metals including copper and brass.

It is another object of this invention to provide new and corrosion inhibiting methods for ferrous metals including iron and steel and non-ferrous metals including copper and brass in contact with an aqueous corrosive medium.

It is another object of this invention to provide new and corrosion inhibiting methods for ferrous metals including iron and steel and non-ferrous metals including copper and brass in contact with an aqueous corrosive medium.

It is another object of this invention to provide new corrosion inhibiting methods for ferrous metals includ-' ing iron and steel and non-ferrous metals including copper and brass in contact with cooling waters.

Other advantages and objects of the present invention will be apparent from the following discussion and appended claims.

It has been found that certain organo-phosphorus compounds, i.e., substituted ethane diphosphonic acids and their salts, unexpectedly function as corrosion inhibitors when used alone or in combination with zinc,

dichromate, certain thiols and 1,2,3-triazoles and mix-,

tures thereof in aqueous or water systems containing metals or in contact with metals.

These substituted ethane diphosphonic acids and their slats have the following generic formula: (I)

R1 R2 i 'OR3 i R3 H,,UO

P-om

In the above Formula I, R, can be from t he g foufix ygen; halogen; hydroxy; CN; -N(R where R, is from the group hydrogen and alkyl containingfrom one to 30 carbon atoms, preferably from one to eight carbon atomsand more preferably from one to four carbon atoms; -XR where X is from the group oxygen and sulfur and R is from the group alkyl containing from one to 30 carbon atoms, preferably one to eight carbon atoms, more preferably one to four carbon atoms; C H (phenyl) and CI'I 'C H (benzyl); acetoxy; SO R., where R, is the same as defined above; benzoyl; -CO H; and CI-I(COOR where R is an alkyl group containing from one to 30 carbon atoms, preferably from one to eight carbon atoms, and more preferably from one to four carbon atoms.

In the aforegoing general Formula I, R is from the group R,, except oxygen, and hydrogen. It is to be understood that R, then is never oxygen and R is only hydrogen when R, is oxygen. Additionally, it is to be understood that in all cases, except when R, is oxygen and R is hydrogen, at least R, or R is a hydroxy group. In other words and for exemplary purposes only, when R, is chlorine, R must be a hydroxy group.

' In conjunction with the proviso that R, is only hydrogen when R, is oxygen with reference to the aforegoing general Formula I, n is an integer having a value of l or 2 and n is only 1 when R, is oxygen.

' In Formula I, R, is from the group metal ions and hydrogen. The aforementioned metal ions are from the group of cations which are capable of forming a water soluble salt and which includes without limitation alkali metals such as sodium, lithium and potassium; ammonium ions; and alkyl ammonium ions. In particular, those alkyl ammonium ions derived from amines having a low molecular weight, such as below about 300, and more particularly the alkyl amines, alkylene amines, and alkanol amines containing not more than two amine groups, such as ethyl amine, diethyl amine, propyl amine, propylene diamine, hexyl amine, Z-ethylhexylamine, N-butylethanol amine, triethanol amine, and the like, are the preferred amines. It is to be understood that all of the compounds falling within the above Formula l and as heretofore defined are generically described herein as ethane diphosphonates. In other words, then, the acids, salts and mistures thereof are all generically described herein as ethane diphosphonates.

In general, the ethane diphosphonates are prepared by contacting an epoxy ethane diphosphonate having the following formula:

wherein R is the same as defined above, with a de-oxiranization agent which opens the ring of said epoxy compound (and provides the substituents on the carbon atoms) to form the ethane diphosphonates falling within Formula I. It is to be understood that the term epoxy ethane diphosphonate used herein generically describes and encompasses the acid and salt forms, and said term is designated at times herein EEDP for the sake of brevity.

The de-oxiranization agents which effect this ring opening are from the group water, ammonia, primary amines, secondary amines, acids, malonates, alcohols, mercaptans, Lewis acid catalysts and mixtures thereof. The specific application of these de-oxiranization agents are disclosed in the processes which are described hereinafter.

In conjunction with the water agent, this ring opening of EEDP is effected by hydrolysis at a temperature of from about 50C to about 150C with or without an inert diluent and acid catalyst, e.g., (respectively), dioxane and l-lCl.

As illustrative of the ethane diphosphonates which can be prepared according to the aforementioned hydrolysis reaction of EEDP, there may be mentioned, without limitation, the following compounds:

1,2 dihydroxy ethane-1,1-diphosphonic acid disodium 1,2 dihydroxy ethane-l ,l-diphosphonate tetrapotassium 1,2 dihydroxy ethane-1,1-

diphosphonate diammonium 1,2 dihydroxy ethane-1,1-

diphosphonate The de-oxiranization agents ammonia, primary amines and secondary amines are generically equated (R NH and R has the same connotation hereinbefore ascribed. This ammonolysis reaction of (R NH with EEDP is generally conducted at a temperature between about -40C and about 150C under atmospheric conditions,

As illustrative of the ethane diphosphonates which can be prepared according to the aforementioned ammonolysis of EEDP, there may be mentioned, without limitation, the following compounds:

2-amino-l-hydroxyethane-1,l-diphosphonic acid 2-hydroxy-1-aminoethane-l ,l-diphosphonic acid tetrasodium 2-amino-1-hydroxyethane-1,1-

diphosphonate 2-methylamino-l -hydroxyethane-l ,1 -diphosphonic acid Z-diethylamino-1-hydroxyethane-1,l-diphosphonic acid disodium Z-dibutylamino-l-hydroxyethane-1,1-

diphosphonate The acid de-oxiranization agents, designated herein as HZ, relate to certain inorganic and organic acids which effect the ring opening. Specifically, the cation, Z, is from the group halogen (such as chlorine, bromine, fluorine and the like), -CN, acetoxy (CH COO-), sulfonate (80 R, wherein R, has the same connotation as heretofore set forth and is from the group hydrogen and alkyl), benzoyl (C H CO), and carboxy (HOOC--). This acid reaction is generally conducted at a temperature between about 10 and C under atmospheric conditions.

As illustrative of the ethane diphosphonates which can be prepared according to the aforementioned acid reaction with EEDP, there may be mentioned, without limitation, the following compounds:

2-chloro-l-hydroxyethane-l ,l-diphosphonic acid 2-hydroxy-1-chloroethane-1,l-diphosphonic acid dipotassium 2-cyano-1-hydroxyethane-l ,1-

diphosphonate 2-sulfo-1-hydroxyethane-1,1-diphosphonic acid disodium 2-fluoro-1-hydroxyethane-1 ,1-

diphosphonate 2-ethylsulfol -hydroxyethane-l 1 -diphosphonic acid The malonate de-oxiranization agent referred to herein as MHC(COOR wherein R is the same as hereinbefore ascribed and M is an alkali metal such as sodium, can be reacted with EEDP at a temperature between about 5C and about 240C under atmosphere conditions to form said ethane diphosphonates.

As illustrative of the ethane diphosphonates which can be prepared according to the aforementioned malonate reaction with EEDP, there may be mentioned, without limitation, the following compounds:

diethyl (2-hydroxy-2,2-diphosphonoethyl) malonate diethyl (Z-hydroxy-l ,1 -diphosphonoethyl) malonate dibutyl (2-hydroxy-2,Z-diphosphonoethyl) malonate dimethyl (tetrasodium 2-hydroxy-2,2-

diphosphonoethyl) malonate dimethyl (2-hydroxy2,2-diphosphonoethyl) malonic acid .The alcohol and mercaptan de-oxiranization agents, generically referred to herein as R XH, wherein R is the same as hereinbefore ascribed and X is oxygen or sulfur, can be reacted with EEDP at a temperature between 5 and 180C under atmospheric conditions to form said ethane diphosphonates. The alcohols utilized are the monoatomic aliphatic alcohols containing from one to 30 carbon atoms, preferably from one to eight carbon atoms, including the respective isomers thereof. Typical alcohols include, for example, methanol, ethanol, propanol and n-butyl alcohol. It is also within the scope of these processes to utilize alcohols such as phenol and benzyl alcohol. The mercaptans utilized are the aliphatic mercaptans containing from one to about 30 carbon atoms, preferably from one to eight carbon atoms, and include, for exemplary purposes only, methyl mercaptan, ethyl mercaptan, propyl mercaptan and n-butyl mercaptan. The isomers of the various mercaptans are also included herein.

As illustrative of the ethane diphosphonates which can be prepared according to the aforementioned reaction of EEDP with either alcohols or mercaptans, there may be mentioned, without limitation, the following compounds:

22. H C(OCH )C(Ol-l)(PO H hydroxy ethane-1,1-diphosphonic acid 23. l-l C(OH)C(OCH )(PO H 2-hydroxy-lmethoxy ethane-1,1-diphosphonic acid 24. H C(OC H )C(H)(PO Nal-l) disodium 2- ethoxy-l-hydroxy ethane-1,1-diphosphonate 25. H C(SCl-l )C(OH)(PO H 2-thiomethyl-lhydroxy ethane-1,1-diphosphonic acid 26. H C(OC H )C(OH)(PO H 2-phenoxy-lhydroxy ethane-1,1-diphosphonic acid 27. l-l C(SC H )C(Ol-l)(PO H 2-thiophenyl, 1-

hydroxy ethane-1,1-diphosphonic acid The reaction of EEDP in the presence of a metal halide Lewis acid yields the oxy" derivative according to the following equation:

Lewis acid In conjunction with the above reaction, a wide variety of Lewis acids can be utilized in order to effect an acid catalyzed rearrangement of the epoxy ethane diphosphonate. There may be mentioned for exemplary purposes only and without any limitation metal halide Lewis acids such as boron trifluoride, zinc chloride, magnesium bromide, ferric chloride, stannic chloride, titanium chloride, zirconium chloride, aluminum chloride, and the like. In conjunction with the utilization of the Lewis acid for the acid catalyzed rearrangement, it is preferred to first dissolve or suspend the metal halide in a non-aqueous inert aprotic solvent such as nitromethane, dichloromethane, nitrobenzene, nitropropane, chlorobenzene, dichlorobenzene, dichloroethane, tetrachloroethane, perchloroethylene, petroleum ether, carbon tetrachloride, chloroform, carbon disulfide, ethyl ether, benzene and the like, and then contact the resultant solution or slurry with the EEDP material. The amount of solvent utilized is not a limiting factor as long as that amount chosen does not substantially adversely affect the preparation of the desired end product.

The acid catalyzed rearrangement of the epoxy ethane diphosphonate is generally conducted with the epoxy ethane diphosphonate and a lewis acid catalyst (and, if desired, an inert aprotic solvent such as ethyl ether) at a temperature between about and 150C, and under atmospheric conditions. Higher or lower temperatures can be utilized, e.g., as low as 50C and as high as 250C, depending, for example, upon the boiling point of said solvent. It is within the scope of the present invention that super-atmospheric (e.g., from about 1 to 10 atmospheres) and sub-atmospheric (e.g., 5a to 760 mm Hg) conditions and also in an inert atmosphere such as nitrogen or helium may be utilized where one so desires.

The quantity of Lewis acid catalyst utilized in conjunction with the acid catalyzed rearrangement will vary somewhat, depending upon the type of metal halide Lewis acid catalyst utilized, the temperature at which the reaction takes place, and, in some instances, the pressure of the system. lt is to be understood that any amount of Lewis acid catalyst can be utilized as long as that amount is not substantially detrimental to achieving the desired end product. lt is found that from about 0.01 to about 4 mole equivalents of said catalyst for each mole of EEDP starting material suffices to 2-methoxy-ltetrapotassium 2-oxy with hydrogen peroxide (which functions as an epoxidizing agent) in the presence of a catalyst such as sodium tungstate. The above ethylene diphosphonate, also sometimes referred to in ,the art as vinylidene diphosphonate, is known in the art (in its ester form and processes for preparing the same) as exemplified by US. Pat. No. 3,062,792, which is incorporated herein by reference. The ethylene diphosphonic acids and salts per se and processes for preparing the same are described in Canadian patent No. 81 1,736, which is incorporated herein by reference.

It has been found that to effectively inhibit corrosion, at least 1 part per million, preferably from about 10 parts per million (ppm) to about 500 parts per million, more preferably from about 10 parts per million to about 150 parts per million, of the ethane diphosphonate should be utilized in the corrosive medium. It is to be understood that greater than 500 ppm of the ethane diphosphonate can be utilized where one so desires as long as the desired end result is substantially achieved or these higher amounts are not detrimental to the water system.

The ethane diphosphonate corrosion inhibitors of the present invention are effective in both an acidic or basic corrosive media. The pH can range from about 4 to about 12. For Example, 1,2 dihydroxy ethane-1,1- diphosphonic acid used in amounts from about 3 parts per million to about parts per million is an effective corrosion inhibitor in a corrosive medium where the pH is from about 4 to about 12.

In conjunction with the utilization of the ethane ethane diphosphonate, e.g., a suitable corrosion inhibitor may consist of 50 ppm of zinc ion plus 50 ppm of said diphosphonate.) It is to be understood, then, that the present invention also encompasses a corrosion inhibition composition containing a mixture of the ethane diphosphonate and a zinc-containing material (i.e. a water-soluble zinc salt) which is capable of forming the zinc ion in an aqueous solution.

Illustrative examples of the zinc-containing material (water-soluble zinc salt) which are set forth for exemplary purposes only and hence non-restrictive, include zinc acetate, zinc bromate, zinc benzoate, zinc borate, zinc bromide, zinc butyrate, zinc caproate, zinc carbonate, zinc chlorate, zinc chloride, zinc citrate, zinc fluoride, zinc fluosilicate, zinc formate, zinc hydroxide, zinc d-lactate, zinc laurate, zinc permanganage, zinc nitrate, zinc hypophosphite, zinc salicylate, zinc sulfate and zinc sulfite. The preferred water-soluble zinc salt is zinc sulfate. It is to be understood that it is within the scope of the present invention that the zinc ion can be supplied in part or wholly by using the zinc salt of the acid form of the ethane diphosphonate.

The ethane diphosphonate and the zinc containing material, which is, in essence, a water soluble zinc salt, may be mixed as a dry composition and can be fed into a water system containing the metals heretofore described to be protected. Such a composition having maximum synergism between the ethane diphosphonate and the zinc ion containing material comprises from about 10 percent to about 80 percent by weight of the water soluble zinc salt and from about percent to about 90 percent by weight of the ethane diphosphonate, all weights being predicated upon the total weight of the mixture. Preferably the weight of the composition comprises from about 20 percent to about 60 percent by weight of the water soluble zinc salt and from about 40 percent to about 80 percent by weight of the ethane diphosphonate.

A combination of about 3 to 100 ppm of ethane diphosphonate and about 2 to about 100 ppm zinc ion will inhibit corrosion in most water systems; the most preferred concentration range is about 5 to ppm diphosphonate and about 5 to 25 ppm zinc ion. It is to be understood, however, that those concentrations are not in any manner meant to limit the scope of the present invention.

It has also been found that synergism exists between the ethane diphosphonate and chromate or dichromate. Because chromate and dichromate are each readily converted into the other by a change in pH, it is understood that both will be simultaneously present at most pHs, even though only one is mentioned.

Corrosion in most water systems may be inhibited by adding from about 1 to about 100 ppm of the ethane diphosphonate and from about 1 to about 100 ppm of the chromate or dichromate; preferably from about 5 to 25 ppm ethane diphosphonate and from about 5 to 25 ppm chromate or dichromate is added. It is to be understood that larger amounts or smaller amounts of each material can be utilized if one so desires.

Suitable chromates for use in the composition and process of this invention include, for exemplary purposes only, sodium dichromate dihydrate, anhydrous sodium chromate, sodium chromate tetrahydrate, sodium chrom ate hexahydrate, sodium chromate decahydrate, potassium dichromate, potassium chromate, ammonium dichromate, and chromic acid. In other words, the chromium compound used is any water soluble hexavalent compound of chromium and is preferably an alkali metal chromate or dichromate heretofore described.

In most cases an effective corrosion inhibition composition contains a mixture of from about 1 percent to about 60 percent and preferably from about 10 percent to about 40 percent, of the water soluble inorganic chromate, based on the combined weight of the chromate and ethane diphosphonate. The use of chromates per se is further described in U.S. Pat. No. 3,431,217 and the publications cited in this patent, all of which are incorporated herein by reference.

It has also been found that compositions of ethane diphosphonate, zinc ion, and chromate or dichromate are useful in inhibiting the corrosion of metals. The inhibiting action of zinc (supplied in the form of a water soluble zinc salt heretofore mentioned) and dichromate compositions has been shown in U.S. Pat. No. 3,022,133, which is incorporated herein by reference. Thus all three components of this composition are mutually synergistic. The co-action of zinc and dichromate illustrated in U.S. Pat. No. 3,022,133 remains unaffected in the presence of ethane diphosphonate and the other ingredients of the inhibitor compositions mentioned herein. In other words then, it is within the scope of the present invention that a corrosion inhibiting composition contain an ethane diphosphonate, a water soluble zinc salt and a chromate and/or dichromate.

Especially useful combinations of the ethane diphosphonate, chromate and zinc exist in the range of from about 1 to about ppm of the ethane diphosphonate, from about )5 to about 50 ppm of the chromate or dichromate, and from about to 50 ppm of the zinc ion. The preferred range is from about 2 to 30 ppm ethane diphosphonate, and from about 1 to 15 ppm chromate or dichromate, and from about 1 to about 15 ppm zinc ion.

Where the water systems are in contact with copper per se or copper-containing metals, it is desirable to use, along with the ethane diphosphonates (either alone or in combination with the zinc ion and/or dichromate or chromate), 1,2,3-triazoles or a thiol of a thiazole, an oxazole, or an imidazole as described respectively in U.S. Pat. Nos. 2,941,953; 2,742,369; and 3,483,133; all of which patents are incorporated herein by reference. These azoles are referred to herein as thiols and 1,2,3-thiazoles. These thiols and 1,2,3- thiazoles are found effective in inhibiting the attack of the ethane diphosphonate on copper.

The preferred 1,2,3-triazole is 1,2,3-benzotriazole of the formula The preferred thiols of a thiazole, an oxazole, or an imidazole are 2-mercaptothioazole Z-mercaptobenzothiazole SII Z-mercaptobenzoxazole and Z-mercaptobenzimidazole A dry composition may be made which may be fed.

into the water system containing copper. Such a composition would consist of about 20 percent to 90 percent ethane diphosphonate, about 1 percent to percent thiol or 1,2,3-triazole, and up to about 79 percent soluble zinc salt; preferably, it would consist of about 38 percent to 90 percent ethane diphosphonate, about 2 percent to 10 percent thiol or 1,2,3-triazole, and up to about 60 percent soluble zinc salt.

It is within the scope of the present invention that the corrosion inhibitors of this invention may be used in conjunction with various well-known inhibitors such as the molecularly dehydrated phosphates and amino phosphonates (such as those disclosed in U.S. Pat. No. 3,483,133 which is incorporated herein by reference).

In conjunction with the Examples hereinafter set forth, two tests are conducted to determine the effectiveness of the corrosion inhibitors of the present invention in different corrosive media, i.e., ordinary tap water and synthetic cooling tower water.

Test 1 was conducted at room temperature, about 70F, wherein several coupons of mild steel (S.A.E. 1018) having dimensions of 5 cm X 3.5 cm X 0.32 cm were thoroughly cleaned using a commercially available cleansing powder and rinsed with distilled water and acetone. After the coupons were weighed, they were mounted on brackets and continuously immersed and removed from the corrosion composition, i.e., ordinary tap water, so that the coupons remain immersed in the composition for 60 seconds and then remained out of solution, exposed to air for 60 seconds. This procedure was continued for a definite length of time (in hours) after which the coupons were withdrawn and the corrosion products on the coupons were removed by using a soft brush.

The coupons were rinsed with distilled water and acetone and then reweighed. The loss in weight (in milligrams) was then appropriately inserted into the equation:

KW/DAT= Corrosion in mills per year wherein W weight loss during tests in milligrams;

D specific gravity of the metal;

A exposed surface area in square cm; and

T time of exposure to solution in hours -in order to determine the corrosion that has taken place expressed in terms of mills of penetration per year (m.p.y.). The corrosion rate of the coupons protected by a corrosion inhibitor can then be compared to the corrosion rate of the unprotected coupons. A decrease in the corrosion rate indicates the effectiveness of the corrosion inhibitor.

ln tests of this nature where the aqueous corrosive medium is ordinary tap water at room temperature, any corrosion rate less than that corrosion rate of the said medium is desired and rates of less than 5 m.p.y. are highly desired and substances that give this value or lower are considered excellent. This does not mean, however, that substances having a corrosion rate of more than 5 m.p.y. are not valuable; depending upon the particular conditions a compound having a higher corrosion rate may be used, as in an instance where the equipment will be used only for a short period of time.

A cooling water system was constructed on a small scale to approximate actual conditions for Test 2. From a five gallon glass tank containing synthetic cooling water,a hose leads into a 6 in. glass jacket which surrounds a mild steel pipe. A hose leads from the jacket to a glass condenser and then back to the tank. Air is added to the system at the condenser in order to match an actual operation in which air is absorbed by the cooling water. Steam is passed through the steel pipe 200 ppm C i; 55 ppm Na 320 ppm Cl 600 ppm S0. 500 ppm H00,- 58 pp Total Dissolved Solids of Distilled Water 1,733

A circulating cooling-water system contains a high concentration of inorganic salt or ions much higher than ordinary tap water as can be seen from the formulation for synthetic cooling tower water. Likewise a cooling water system is operated at high temperatures usually 50C or higher. Primarily because of these two factors the acceptable corrosion rates in cooling waters is less than 10 m.p.y. therefore corrosion inhibitors having corrosion rates less than 10 m.p.y. are considered good and commercially acceptable.

The corrosion inhibiting compositions of this invention can be manufactured via a number of methods which will give good protection against corrosion. For example, the ethane diphosphonate either in the form of its acid or salt per se or in combination with the water-soluble zinc salt, chromate, dichromate, thiols and 1,2,3-triazole can simply be dissolved by intermixing them into the aqueous corrosive medium. Via another method, they can be dissolved separately in water or another suitable solvent and then intermixed into the aqueous corrosive medium.

Various means are available to insure that the correct proportion of corrosion inhibitor is present in the corrosive medium. For example, a solution containing the said corrosion inhibitor can be metered into the corrosive medium by a drip feeder. Another method is to formulate tablets or briquettes of a solid ethane diphosphonate (and other ingredients) and these can then be added to the corrosive medium. The said solid," after briquetting, can be used in a standard ball feeder so that the solid is released slowly into the corrosive medium.

The invention will be further illustrated but is not limited by the following examples.

EXAMPLEI Three separate portions consisting each of 600 ml of aqueous corrosive medium are individually treated with the indicated ethane diphosphonate so that it contains separately 5, 50, and 100 parts per million of said diphosphonate. Test 1 as described hereinbefore is conducted using 1018 S.A.E. mild steel coupons measuring cm X 3.5 cm X 0.32 cm. The corrosive medium is a sample of water obtained from the St. Louis County Water Company having a pH from about 9.0 to about 9.5 and a hardness of about 100 to about 1 parts per million as calcium carbonate. Test 1 is conducted according to the procedure hereinbefore outlined for 90 hours. 600 ml. of the untreated aqueous corrosive medium is tested as a control. The data are illustrated in Table 1.

Test 1 is also conducted on a commercially available corrosion inhibitor, containing some zinc about 1 to about 4 percent by weight but mostly tetra sodium pyrophosphate about 40 to about 60 percent by weight; these data are shown in Table l.

TABLEl Corrosion Rates on Mild Steel (S.A.E. l0l8) Coupons 5 cm X 3.5 cm X 0.32 cm pH 9.0

7 5O 96 8.3 7 96 5.2 10 5 96 4.7 10 50 96 2.8 10 100 96 2.0 13 5 96 9.8 13 50 96 5.4 13 100 96 3.9 15 5 96 1 1.6 15 50 96 5.0 15 100 96 4.1 20 5 96 6.7 20 50 96 4.2 20 100 96 3.6 24 5 96 9.2 24 50 96 5.8 24 100 96 4.1 29 5 96 10.3 29 50 96 6| 29 100 96 4.4 Corrosion Medium 96 29.6 Zinc-Tetra Sodium Pyrophosphate (Zinc 1% to 5 96 15 4%, tetra sodium pyro- 50 96 6.8 phosphate 40% to 60%) 100 96 4.1

The data in Table 1 show that the ethane diphosphonates are an effective corrosion inhibitor. Table 1 shows that these ethane diphosphonates are at least as good as and in some cases superior to the commercially available zinc tetra sodium pyrophosphate inhibitor. As pointed out before, substances that reduce the corrosion rates of mild steel to less than 5 m.p.y. in ordinary tap water are considered excellent. Therefore, it can readily be appreciated that the ethane diphosphonates of the present invention can be used as a corrosion inhibitor.

EXAMPLE 11 Test 2, as described hereinbefore, is conducted to determine the effectiveness of the indicated ethane diphosphonates (Example 1) as a corrosion inhibitor in cooling water. Example 1 are added to the five gallon tank containing about 16,000 ml. of synthetic cooling tower water (having a flow rate of 2,640 m1./min.), as set forth above, so that said water contains 5, 50, and 100 parts per million of the ethane diphosphonates. The temperature of the synthetic cooling water is 50C. Mild steel coupons (ASTM A-285) measuring 2.5 cm X 5 cm X .6 cm are cleaned with a commercially available cleansing powder and weighed. They are then mounted on brackets in the five gallon tank. After exposure, they are reweighed and their corrosion rates are calculated.

A blank solution containing no ethane diphosphonate is used as a control to determine the corrosion rates of mild steel coupons in untreated synthetic cooling tower water.

The data show that the ethane diphosphonate corrosion inhititors at greater than 50 ppm reduce the corro sion rate to less than 10 m.p.y. (the control corrosion medium is about 24.6 m.p.y.), which is the generally acceptable rate for a corrosion inhibitor.

A visible inspection of the mild steel pipe through which the steam passes and which is cooled by the synthetic cooling water treated with ethane diphosphonates shows a very minute amount of corrosion, another indication of the effectiveness of the novel compound of the present invention.

A commercial corrosion inhibitor containing 2 percent to 4 percent by weight of zinc and 40 percent to 60 percent by weight of tetra sodium pyrophosphate, is used to treat the synthetic cooling water and is tested in the same manner as Example II. The corrosion rates of the coupons are more than m.p.y. and a significant amount of corrosion forms on the mild steel pipe through which the steam passes.

It can readily be appreciated that the ethane diphosphonates are good corrosion inhibitors when used in cooling waters and especially when used in heat-exchanging systems.

EXAMPLE III Example I (above) is repeated with the exception that in addition to the ethane diphosphonate (5, 50 and 100 ppm) corrosion inhibitor, there is added sufficient amounts of zinc sulfate in order to provide respectively 5, 50 and 100 ppm of zinc ion in the corrosion medium. The synergistic corrosion inhibitor, i.e., the indicated ethane diphosphonate plus the zinc sulfate, shows that at all three concentrations (i.e. 5, 50 and 100 ppm of each), the corrosion rates are substantially less than the rates using the corrosion medium without this mixture and is on the average 30 percent less than those rates obtained using only the ethane diphosphonate per se.

EXAMPLE IV Example I (above) is repeated with the exception that in addition to the ethane diphosphonate (5, 50 and 100 ppm) corrosion inhibitor, there is added respectively 5, 50 and 100 ppm sodium dichromate to the corrosion medium. The synergistic corrosion inhibitor, i.e., the indicated ethane diphosphonate plus the sodium dichromate, shows that at all three concentrations (i.e. 5, 50 and 100 ppm of each), the corrosion rate is less than the rate using the corrosion medium without this mixture and is on the average about 15 to 25 percent less than those rates obtained using only the ethane diphosphonate per se.

EXAMPLE V shows that the corrosion rates using this mixture are substantially less than the rates using the corrosion medium without this mixture and is on the average about 30 percent to 40 percent less than those rates obtained using only the ethane diphosphonate per se.

EXAMPLE VI The corrosion inhibitors as described in the above Examples I, III, IV and V are separately and individually tested in boiler water for their separate corrosive inhibiting effect on red brass and mild steel. The boiler water contains approximately 30-60 parts per million phosphate and approximately 30-60 parts per million sulfate having a pH of about 14. The corrosive tests are carried out at a temperature of 314 C at 1,500 psig and with a 50 parts per million of the respective corrosion inhibitor. In each test, approximately 1 liter of boiler blow-down water is charged into a 2 liter bomb and 1 ml. of a stock solution is added to give approximately 50 parts per million of the corrosion inhibitor. Duplicate coupons of mild steel and red brass measuring 5 cm X 3.5 cm X 0.32 cm are scrubbed with a commercially available cleansing powder and weighed. The coupons are then mounted on insulated brackets so that two coupons are in the liquid phase and two coupons are in the vapor phase. After sealing the bomb, the cycle of pumping down with a vacuum pump and filling with nitrogen is repeated four times.

The time of the tests are taken to be roughly from the time the temperature reached 150C after starting to heat till it again reached this temperature after turning off the heat.

The results of these tests show that at temperatures above 300C the respective corrosion inhibitors significantly reduces the corrosion rates of both red brass and mild steel either completely immersed in the cooling waters or in contact with the vapors of a cooling water system containing the complex. It also demonstrates the stability of the corrosion inhibitors of the present invention at elevated temperatures, over 300C, for extended periods of time.

In each of the following examples, the ethane diphosphonate and zinc compound are added to the aqueous corrosive medium so that 50 parts per million of each is present.

EXAMPLE VII Ingredients Parts- Aqueous corrosive medium 75,000 1,2 dihydroxy ethane'l ,l-diphosphonic acid 2 Zinc sulfate 2 EXAMPLE VIII Ingredients Parts Aqueous corrosive medium 80,000 2-aminol -hydroxyethanel l -diphosphonic acid 2.6 Zinc sulfate 2.6

EXAMPLE IX Ingredients Parts Aqueous corrosive medium 90,000 2-chlorol -hydroxyethane-1 ,1 -diphosphonic acid 2.3 Zinc sulfate 2.3

EXAMPLE X Ingredients Parts Aqueous corrosive medium 90,000 2-sulfol -hydroxyethanel l -diphosphonic acid 2.3 Zinc sulfate 2.3

EXAMPLE XI Ingredients Parts Aqueous corrosive medium 90 ,000 diethyl (Z-hydroxy-Z,2-diphosphonoethyl) malonate 2.3 Zinc sulfate 2.3

EXAMPLE XII Ingredients Parts Aqueous corrosive medium ,000 dipotassium Z-cyano-l -hydroxyethane- 1,1-diphosphate 1.6 Zinc sulfate 1.6

EXAMPLE XIII Ingredients Parts Aqueous corrosive medium I 1,000 Z-methoxy-l-hydroxy ethanel ,l-

diphosphonic acid 2.7

Zinc sulfate 2.7

EXAM PLE XIV lngredients Parts Aqueous corrosive medium 100,000 Lthiomethyll -hydroxyethane-l ,l

diphosphonic acid 2.5 Zinc sulfate 2.5

Tests 1 and 2 were conducted on each of the abovetreated aqueous corrosive media. The corrosion rates in all instances were lower than the untreated corrosive media.

EXAMPLE XV A compressed ball of a standard weight and dimension is prepared containing the following ingredients in the quantities noted.

1,2 dihydroxy ethane-l ,l-diphosphonic acid 34 Lignosulfite binder (bindarene 8 Zinc sulfate l6 Inert Ingredients 42 The above composition after briquetting is suitable for mechanically measured addition in water treatment wherein a ball feeder is employed.

EXAMPLE XVI Example I (above) is repeated with the exception that copper coupons are used instead of mild steel coupons and sufficient amounts of 1,2,3-benzotriazole to provide 1, and 10 ppm thereof in the corrosive media is used in addition to the ethane diphosphonate. Example XVI is repeated again but without the benzotriazole material. The data shows that when copper coupons are used and the corrosive media contains the indicated ethane diphosphonate, the corrosion rates are less than when the corrosion media does not contain said diphosphonate. The data further shows that use of the benzotriazole with the ethane diphosphonate further reduces the corrosion rate.

Thus, it may be seen that this invention relates to ethane diphosphonates as corrosion inhibitors. We do not intend to be limited to any compounds, composition, or methods disclosed herein for illustrative purposes. Our invention may be otherwise practiced and embodied within the scope of the following claims.

What is claimed is:

l. A composition useful for inhibiting the corrosion of metals in a water system comprising from about 10 percent to about 80 percent by weight of a water soluble zinc salt and from about percent to 90 percent by weight of an ethane diphosphonate having the formula wherein a. R, is selected from the group consisting of oxygen; halogen; hydroxy; -CN; N(B wherein R is selected from the group consisting of hydrogen and alkyl; -XR wherein X is selected from the group consisting of oxygen and sulfur and R is selected from the group consisting of alkyl, C, H and C, H,; acetoxy; 50 R wherein R is the same as defined above; benzoyl; -CO H and 6 cooRs c 0 012, wherein R is an alkyl group containing from one to 30 carbon atoms.

b. R is selected from the group consisting of R,, ex-

cept oxygen; and hydrogen; with the proviso that R is only hydrogen when R, is oxygen; and with the proviso that in all cases, except when R, is oxygen and R2 is hydrogen, at least R, or R2 is hydroxy;

c. R,, is selected from the group consisting of hydrogen, cations which are capable of forming a water soluble salt and mixtures thereof; and

d. n is an integer having a value of l or 2 and n is I when R, is oxygen.

2. The composition as set forth in claim 1 wherein R is hydrogen.

3. The composition as set forth in claim 1 wherein R is a cation selected from the group consisting of alkali metals, zinc, and mixtures thereof.

4. The composition as set forth in claim 1 wherein R, and R are either hydroxy or N(R.,) groups with the proviso that neither R, nor R are alike.

5. The composition as set forth in claim 1 wherein R, and R are either )(R or hydroxy groups with the proviso that neither R, m are alike.

6. The composition as set forth in claim 1 wherein R, and R are either CN or hydroxy with the proviso that neither R, nor R are alike.

7. The composition as set forth in claim 1 wherein R, and R are both hydroxy groups.

8. The composition as set forth in claim 1 wherein R, and R are either hydroxy or SO R with the proviso that neither R, nor R are alike.

9. The composition as set forth in claim 1 wherein R, and R are either halogen or hydroxy with the proviso that neither R, nor R are alike.

10. The composition as set forth in claim 1 wherein R, and R are either hydroxy or g cooR,, ooom with the proviso that neither R, nor R are alike.

11. The composition as set forth in claim 7 wherein the water soluble zinc salt is zinc sulfate and R is hydrogen.

12. The composition as set forth in claim 1 and additionally containing a water-soluble hexavalent compound of chromium.

13. A composition useful for inhibiting the corrosion of metals in a water system which contains cuprous metals comprising 1. from about 20 percent to about percent by weight of an ethane diphosphonate having the formula wherein a. R, is selected from the group consisting of oxygen; halogen; hydroxy; CN; N(R,,)

wherein R, is selected from the group consisting OOORa COORs wherein R is an alkyl group containing fro one to 30 carbon atoms. b. R is selected from the group consisting of R,, except oxygen; and hydrogen; with the proviso that R, is only hydrogen when R, is oxygen; and

with the proviso that in all cases, except when R,

is oxygen and R is hydrogen, at least R, or R is hydroxy; 0. R is selected from the group consisting of hydrogen cations which are capable of forming a water soluble salt and mixtures thereof; and n is an integer having a value of i or 2 and n is 1 when R, is oxygen.

2. from about 1 percent to about 10 percent by weight of a compound selected from the group consisting of l, 2, 3 triazoles, thiols of thiazoles, thiols of oxazoles, thiols of imidazoles, and mixtures thereof, and

3. up to about 79 percent by weight of a water soluble zinc salt.

14. The composition as set forth in claim 13 wherein the diphosphonate is selected from the group consisting of 1,2-dihydroxyethane-l ,1 diphosphonic acid;

Dipotassium 2-cyano-lhydroxyethane-l ,1-

diphosphonate;

Disodium 2-butyl amino-l-hydroxyethane-l ,l-

diphosphonate;

Dibutyl 2-hydroxy-2,2-diphosphono ethylmalonate;

2-thiomethyl- 1 hydroxyethane-l l diphosphonic acid; and

2-oxyethane-l ,l-diphosphonic acid.

15. The composition as set forth in claim 13 and additionally containing a water-soluble hexavalent compound of chromium.

16. A method of inhibiting the corrosion of metals-in a water system comprising maintaining in the water of said system at least 3 parts per million of an ethane diphosphonate having the formula wherein a. R, is selected from the group consisting of oxygen; halogen; hydroxy; CN; N(R.,) wherein R is selected from the group consisting of hydrogen and alkyl; XR wherein X is selected from the group consisting of oxygen and sulfur and R is selected from the group consisting of alkyl, C ll and C-,H acetoxy; -SO R., wherein R, is the same as defined above; ben'zoyl; CO H; and

coon,

wherein R is an alkyl group containing from one to 30 carbon atoms.

. R is selected from the group consisting of R,-, ex-

cept oxygen; and hydrogen; with the proviso that R, is only hydrogen when R, is oxygen; and with the proviso that in all cases, except when R, is oxygen and R is hydrogen, at least R, or R is hydroxy;

c. R, is selected from the group consisting of hydrogen, cations which are capable of forming a water soluble salt and mixtures thereof; and

d. n is an integer having a value of l or 2 and n is 1 when R, is oxygen.

17. The method as set forth in claim 16 wherein R is hydrogen.

18. The method as set forth in claim 16 wherein R is a metal ion selected from the group consisting of alkali metals, alkaline earth metals, aluminum, zinc, calcium, manganese and mixtures thereof.

19. The method as set forth in claim 16 wherein R, and R are either hydroxy or N(R,,) groups with the proviso that neither R, nor R are alike. Y

20. The method as set forth in claim 16 wherein R, and R are either -XR or hydroxy groups with the proviso that neither R, nor R are alike.

2]. The method as set forth in claim 16 wherein R, and R, are either -CN or hydroxy with the proviso that neither R, nor R are alike.

22. The method as set forth in claim 16 wherein R, and R are both hydroxy groups.

23. The method as set forth in claim 16 wherein R, and R are either hydroxy or SO R with the proviso that neither R, nor R are alike.

24. The method as set forth in claim 16 wherein R, and R are either halogen or hydroxy with the proviso that neither R, nor R are alike.

25. The method as set forth in claim 16 wherein R,

and R are either hydroxy or COORB COORB salt.

31. A method of inhibiting metal corrosion in a water system containing metals comprising maintaining in the water of said system (a) from about 3 to about ppm of l, 2 dihydroxy ethane-1,1-diphosphonic acid or its water soluble salts and (b) up to about 100 ppm zinc ion derived from water soluble zinc salts.

Notice of Adverse Decision in Interference In Interference No. 99,968, involving Patent No. 3,714,066, T. M. King and H. L. Vandersall, METHODS OF INHIBITING CORROSION WITH ETH- ANE DIPHOSPHONATE COMPOSITIONS, final judgment adverse to the patentees was rendered Dec. 11, 1980, as to claims 1, 2, and 3.

[Official Gazette June 2, 1981.]

Notice of Adverse Decision in Interference In Interference No. 99,968, involving Patent No. 3,714,066, T. M. King and H. L. Vandersall, METHODS OF INHIBITING CORROSION WITH ETH- ANE DIPHOSPHONATE COMPOSITIONS, final judgment adverse to the patentees was rendered Dec. 11, 1980, as to claims 1, 2, and 3.

[Official Gazette June 2, 1981.] 

1. A composition useful for inhibiting the corrosion of metals in a water system comprising from about 10 percent to about 80 percent by weight of a water soluble zinc salt and from about 20 percent to 90 percent by weight of an ethane diphosphonate having the formula
 1. from about 20 percent to about 90 percent by weight of an ethane diphosphonate having the formula
 2. The composition as set forth in claim 1 wherein R3 is hydrogen.
 2. from about 1 percent to about 10 percent by weight of a compound selected from the group consisting of 1, 2, 3 -triazoles, thiols of thiazoles, thiols of oxazoles, thiols of imidazoles, and mixtures thereof, and
 3. The composition as set forth in claim 1 wherein R3 is a cation selected from the group consisting of alkali metals, zinc, and mixtures thereof.
 3. up to about 79 percent by weight of a water soluble zinc salt.
 4. The composition as set forth in claim 1 wherein R1 and R2 are either hydroxy or -N(R4)2 groups with the proviso that neither R1 nor R2 are alike.
 5. The composition as set forth in claim 1 wherein R1 and R2 are either -XR5 or hydroxy groups with the proviso that neither R1 nor R2 are alike.
 6. The composition as set forth in claim 1 wherein R1 and R2 are either -CN or hydroxy with the proviso that neither R1 nor R2 are alike.
 7. The composition as set forth in claim 1 wherein R1 and R2 are both hydroxy groups.
 8. The composition as set forth in claim 1 wherein R1 and R2 are either hydroxy or -SO3R6 with the proviso that neither R1 nor R2 are alike.
 9. The composition as set forth in claim 1 wherein R1 and R2 are either halogen or hydroxy with the proviso that neither R1 nor R2 are alike.
 10. The composition as set forth in claim 1 wherein R1 and R2 are either hydroxy or with the proviso that neither R1 nor R2 are alike.
 11. The composition as set forth in claim 7 wherein the water soluble zinc salt is zinc sulfate and R3 is hydrogen.
 12. The composition as set forth in claim 1 and additionally containing a water-soluble hexavalent compound of chromium.
 13. A composition useful for inhibiting the corrosion of metals in a water system which contains cuprous metals comprising
 14. The composition as set forth in claim 13 wherein the diphosphonate is selected from the group consisting of 1,2-dihydroxyethane-1,1-diphosphonic acid; Dipotassium 2-cyano-1-hydroxyethane-1,1-diphosphonate; Disodium 2-butyl amino-1-hydroxyethane-1,1-diphosphonate; Dibutyl 2-hydroxy-2,2-diphosphono ethylmalonate; 2-thiomethyl-1-hydroxyethane-1,1-diphosphonic acid; and 2-oxyethane-1,1-diphosphonic acid.
 15. The composition as set forth in claim 13 and additionally containing a water-soluble hexavalent compound of chromium.
 16. A method of inhibiting the corrosion of metals in a water system comprising maintaining in the water of said system at least 3 parts per million of an ethane diphosphonate having the formula
 17. The method as set forth in claim 16 wherein R3 is hydrogen.
 18. The method as set forth in claim 16 wherein R3 is a metal ion selected from the group consisting of alkali metals, alkaline earth metals, aluminum, zinc, calcium, manganese and mixtures thereof.
 19. The method as set forth in claim 16 wherein R1 and R2 are either hydroxy or -N(R4)2 groups with the proviso that neither R1 nor R2 are alike.
 20. The method as set forth in cLaim 16 wherein R1 and R2 are either -XR5 or hydroxy groups with the proviso that neither R1 nor R2 are alike.
 21. The method as set forth in claim 16 wherein R1 and R2 are either -CN or hydroxy with the proviso that neither R1 nor R2 are alike.
 22. The method as set forth in claim 16 wherein R1 and R2 are both hydroxy groups.
 23. The method as set forth in claim 16 wherein R1 and R2 are either hydroxy or -SO3R6 with the proviso that neither R1 nor R2 are alike.
 24. The method as set forth in claim 16 wherein R1 and R2 are either halogen or hydroxy with the proviso that neither R1 nor R2 are alike.
 25. The method as set forth in claim 16 wherein R1 and R2 are either hydroxy or with the proviso that neither R1 nor R2 are alike.
 26. The method as set forth in claim 16 and additionally containing in said system a water soluble hexavalent compound of chromium.
 27. The method as set forth in claim 16 and additionally containing in said system a water soluble zinc salt.
 28. The method as set forth in claim 16 and additionally containing in said system a water soluble hexavalent compound of chromium and a water soluble zinc salt.
 29. The method as set forth in claim 16 wherein said system contains cuprous metals and the water system additionally contains a compound selected from the group consisting of 1, 2, 3 - triazoles, thiols of thiazoles, thiols of oxazoles, thiols of imidazoles, and mixtures thereof.
 30. The method as set forth in claim 29 wherein the water system additionally contains a water soluble zinc salt. 